Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/041—Carbon nanotubes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/042—Graphene or derivatives, e.g. graphene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives

Definitions

• the invention relates to a thermoplastic molding composition which contains at least one thermoplastic matrix polymer, at least one hyperbranched or hyperbranched polymer and conductive carbon fillers.
• the WO2009 / 077492 discloses polyamide monocomposites.
• the WO 2009/115536 relates to polyamide nanocomposites with hyperbranched polyethyleneimines.
• the thermoplastic molding compositions described comprise at least one thermoplastic polyamide, at least one hyperbranched polyethyleneimine, at least one amorphous oxide and / or hydrated oxide of at least one metal or semimetal having a number-weighted average diameter of the primary particles of 0.5 to 20 nm, wherein the molding materials as fillers and carbon Nanotubes may contain.
• pigments carbon black and graphite can be used.
• the hyperbranched polyethylenimines are used to reduce the melt viscosity with simultaneously favorable mechanical properties.
• the WO 2008/074687 relates to thermoplastic molding compositions with improved ductility.
• the molding compositions comprise a partially aromatic polyamide, a copolymer of ethylene, 1-octene or 1-butene or propene or mixtures thereof and functional monomers in which the functional group is selected from carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide, carboxylic acid imide , Amino, hydroxyl, epoxy, urethane or oxazoline groups or mixtures thereof.
• the molding compositions may additionally contain fibrous or particulate fillers and highly branched or hyperbranched polycarbonates or highly branched or hyperbranched polyesters.
• an electrically conductive additive can be used, which is selected for example from carbon nanotubes, graphite or Leitruß. Pigments such as carbon black can also be used.
• the hyperbranched or hyperbranched polycarbonates or polyesters are used to improve flowability and ductility.
• the EP-A-2 151 415 describes the use of special hyperbranched polymers which have a triarylamine structure but contain no functional groups capable of reacting with a matrix polymer as a solubilizer for carbon nanotubes.
• the solubilizates thus obtained can be incorporated in polymer resins, including polyamide resins or polycarbonate resins.
• thermoplastic matrix polymers In order to achieve sufficient conductivity in thermoplastic matrix polymers, it is usually necessary to add high amounts of conductivity-improving fillers, such as carbon nanotubes or conductive carbon black. As a result, the mechanical properties of the thermoplastic polymer matrix are often severely impaired. In addition, the use of large quantities of these conductivity-improving fillers is very expensive.
• thermoplastic polymer molding compositions containing conductive carbon fillers which have improved conductivity or in which, while retaining conductivity, the content of carbon fillers can be reduced.
• thermoplastic molding composition containing at least one thermoplastic matrix polymer as component A selected is from polyamides, polyesters, polyacetals and polysulfones and also as a polymer blend can be present and conductive carbon fillers selected from carbon nanotubes, graphenes, or mixtures thereof, as component C, to increase the conductivity of the thermoplastic molding composition.
• thermoplastic molding compositions leads to a significant increase in the electrical conductivity.
• the highly branched or hyperbranched polymer has functional groups which are reactive with the matrix polymer. The improvement of the electrical properties allows the formulation of materials that have a reduced content of conductive fillers.
• the proportion of component B in the thermoplastic molding compositions according to the invention is 0.1 to 5 wt .-%, preferably 0.2 to 3 wt .-%, in particular 0.3 to 1.3 wt .-%.
• the highly branched or hyperbranched polymers of component B have functional groups which are reactive with the matrix polymer of component A. They are capable of reacting under the conditions of shaping the thermoplastic molding composition, for example when molding the thermoplastic molding composition, melting the thermoplastic molding composition, processing the thermoplastic molding composition in an extruder or kneader or pressing tool. In this case, preferably under the processing conditions, in particular during extrusion, a change in molecular weight, preferably a molecular weight, for example visible by increasing the melt or solution viscosity.
• thermoplastic molding compound with the components A, B and C is preferably reactive. It is considered to be reactive if a substantial change in molecular weight or melt viscosity or solution viscosity is observed after mixing, in particular, components A and B, for example in an extrusion. A change is considered essential if the change in the measured value is above the standard deviation of a corresponding measured value.
• the highly branched or hyperbranched polymer of component B should therefore be matched to the matrix polymer of component A, so that reaction of the functional groups is possible.
• Hyperbranched are compounds in which the degree of branching, i. H. the sum of the average number of dendritic linkages and terminal units divided by the sum of the average number of total linkages (dendritic, linear and terminal linkages) multiplied by 100, 10 to 98%, preferably 25 to 90%, particularly preferably 30 to 80% , is.
• DB (%) 100 ⁇ (T + Z) / (T + Z + L), where T is the average number of terminally bound monomer units, Z is the average number of branching monomer units and L is the average number of linearly bound monomer units in the macromolecules of the respective substances, from 10 to 98%, preferably from 25 to 90% and particularly preferred from 30 to 80%.
• Hyperbranched polymers also called hyperbranched polymers, are to be distinguished from the dendrimers.
• Dendrimers are polymers with perfectly symmetrical structure and can be prepared starting from a central molecule by controlled stepwise linking of two or more difunctional or polyfunctional monomers with each already bound monomer. In this case, the number of monomer end groups (and thus the linkages) multiplies with each linking step, and polymers are obtained with tree-like structures, ideally spherical, whose branches each contain exactly the same number of monomer units. Due to this perfect structure, the polymer properties are advantageous in many cases, for example, one observes a low viscosity and a high reactivity due to the high number of functional groups on the spherical surface.
• manufacturing is complicated by the need to introduce and remove protecting groups at each linking step and to require purification operations, which is why dendrimers are usually only produced on a laboratory scale.
• hyperbranched in the context of the present invention comprises the term hyperbranched and is used in the following as representing both terms.
• the hyperbranched polymers have not only perfect dendritic structures but also linear polymer chains and unequal polymer branches which, however, does not significantly degrade the polymer properties compared to those of the perfect dendrimer.
• the hyperbranched polymers used according to the invention differ from the dendrimers.
• a dendrimer has the maximum possible number of branch points, which can be achieved only by a highly symmetrical structure.
• Hyperbranched polymers are thus understood in the context of this invention to mean essentially uncrosslinked macromolecules which are structurally as well as molecularly nonuniform.
• a highly functional hyperbranched polyethyleneimine is to be understood as meaning a product which, in addition to secondary and tertiary amino groups which form the polymer backbone, also has on average at least three, preferably at least six, particularly preferably at least ten functional groups.
• the functional groups are preferably primary amino groups.
• the number of terminal or pendant functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility.
• the highly functional hyperbranched polyethyleneimines of the present invention preferably have not more than 500 terminal or pendant functional groups, especially not more than 100 terminal or pendant groups.
• polyethyleneimines are to be understood as meaning both homo- and copolymers which are prepared, for example, by the processes in Ullmann's Encyclopaedia of Industrial Chemistry, "Aziridines", electronic release (Article published on 15.12.2006 ) or according to WO-A 94/12560 are available.
• the homopolymers are preferably obtainable by polymerization of ethyleneimine (aziridine) in aqueous or organic solution in the presence of acid-releasing compounds, acids or Lewis acids.
• Such homopolymers are branched polymers, which usually contain primary, secondary and tertiary amino groups in the ratio of about 30% to 40% to 30%. The distribution of the amino groups can be determined by means of 13 C-NMR spectroscopy.
• Comonomers used are preferably compounds which have at least two amino functions.
• suitable comonomers are alkylenediamines having 2 to 10 C atoms in the alkylene radical, with ethylenediamine and propylenediamine being preferred.
• Further suitable comonomers are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
• Polyethyleneimines usually have a weight average molecular weight in the range of 100 to 3,000,000, especially 800 to 2,000,000 g / mol.
• the polyethyleneimines obtained by catalyzed polymerization of aziridines usually have a weight-average molecular weight in the range from 800 to 50,000 g / mol, in particular from 1,000 to 30,000 g / mol.
• Higher molecular weight polyethyleneimines are in particular by reaction of said polyethyleneimines with di-functional alkylating compounds such as Chlormethyloxiran or 1, 2-dichloroethane or by ultrafiltration of polymers having a broad molecular weight distribution, such as in EP-A-0 873 371 and EP-A-1 177 035 described or obtainable by crosslinking.
• crosslinked polyethyleneimines which are obtainable by reaction of polyethyleneimines with bifunctional or polyfunctional crosslinkers which have as functional group at least one halohydrin, glycidyl, aziridine, isocyanate unit or a halogen atom.
• examples include epichlorohydrin or bischlorohydrin of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units and in the DE-A 19 93 17 20 and US 4,144,123 called compounds listed.
• Processes for the preparation of crosslinked polyethyleneimines are, inter alia, from the above-mentioned publications as well EP-A 895 521 and EP-A 25515 known.
• Crosslinked polyethyleneimines usually have an average molecular weight of more than 20,000 g / mol.
• grafted polyethyleneimines are also suitable as component B)
• grafted polyethyleneimines it being possible for all compounds which can react with the amino or imino groups of the polyethyleneimines to be used as the grafting agent.
• Suitable grafting agents and processes for the preparation of grafted polyethyleneimines are, for example, the EP-A 675 914 refer to.
• suitable polyethyleneimines are amidated polymers which are usually obtainable by reaction of polyethyleneimines with carboxylic acids, their esters or anhydrides, carboxamides or carboxylic acid halides.
• carboxylic acids their esters or anhydrides, carboxamides or carboxylic acid halides.
• amidated Polymers are subsequently crosslinked with said crosslinkers.
• up to 30% of the amino functions are amidated, so that sufficient primary and / or secondary nitrogen atoms are available for a subsequent crosslinking reaction.
• alkoxylated polyethyleneimines which are obtainable, for example, by reacting polyethyleneimine with ethylene oxide and / or propylene oxide and / or butylene oxide. Such alkoxylated polymers are also crosslinkable.
• Polyethyleneimines which are suitable as component B) include hydroxyl-containing polyethyleneimines and amphoteric polyethyleneimines (incorporation of anionic groups) and lipophilic polyethyleneimines which are generally obtained by incorporation of long-chain hydrocarbon radicals into the polymer chain. Processes for the preparation of such polyethyleneimines are known to the person skilled in the art, so that further details are unnecessary.
• suitable polyethyleneimines may be applied to the WO 2009/115536 , in particular pages 8 to 11, referenced.
• the component (B) can be used as such or as a solution, in particular as an aqueous solution.
• Component B) preferably has a weight-average molecular weight, determined by light scattering, of from 800 to 50,000 g / mol, particularly preferably from 1000 to 40,000 g / mol, in particular from 1200 to 30,000 g / mol.
• the weight average molecular weight is preferably determined by gel permeation chromatography using pullulan as standard in an aqueous solution (water, 0.02 mol / liter formic acid, 0.2 mol / liter KCl).
• component B) preferably has a glass transition temperature of less than 50 ° C., particularly preferably less than 30 ° C. and in particular less than 10 ° C.
• component B) A determined according to DIN 53176 amine number of component B) in the range of 50 to 1000 mg KOH / g is favorable.
• component B) has an amine number of 100 to 900 mg KOH / g according to DIN 53176, very preferably from 150 to 800 mg KOH / g.
• component B it is also possible to use highly branched or hyperbranched polyetheramines.
• suitable polyetheramines are described for example in WO 2009/077492 , there as component B), see pages 6 to 16 there.
• the molding compositions of the invention may also contain a highly branched or hyperbranched polycarbonate having an OH number of 1 to 600, preferably 10 to 550 and especially 50 to 550 mg KOH / g polycarbonate (according to DIN 53240, part 2).
• Hyperbranched polycarbonates are understood as meaning uncrosslinked macromolecules having hydroxyl and carbonate groups which are structurally as well as molecularly nonuniform. They can be based on a central molecule analogous to dendrimers, but with nonuniform chain length of the ester, be constructed. They can also be constructed linearly, with functional side groups, or, as a combination of both extremes, linear and branched molecular parts.
• Hyperbranched polyesters contain, in contrast to the polycarbonates in addition to hydroxyl groups carboxyl groups.
• thermoplastic molding compositions having conductive carbon fillers are excluded according to the invention.
• thermoplastic molding compositions of the invention comprise as component A at least one thermoplastic matrix polymer selected from polyamides, polyesters, polyacetals and polysulfones, which may also be present as a polymer blend.
• At least one polyamide, copolyamide or polyamide-containing polymer blend can preferably be used as component A.
• the polyamides used according to the invention are prepared by reacting starting monomers which are selected, for example, from dicarboxylic acids and diamines or salts from the dicarboxylic acids and diamines, from aminocarboxylic acids, aminonitriles, lactams and mixtures thereof. These may be starting monomers of any desired polyamides, for example aliphatic, partially aromatic or aromatic polyamides.
• the polyamides can amorphous, crystalline or partially crystalline.
• the polyamides may also have any suitable viscosities or molecular weights. Particularly suitable are polyamides with aliphatic, partially crystalline or partially aromatic, and amorphous structure of any kind.
• Such polyamides generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. according to ISO 307.
• Examples include polyamides derived from lactams having 7 to 11 ring members, such as polycaprolactam and polycapryllactam, as well as polyamides obtained by reacting dicarboxylic acids with diamines.
• alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used.
• Suitable diamines are, in particular, alkanediamines having 2 to 12, in particular 6 to 8, carbon atoms and also m-xylylenediamine, di- (4-aminophenyl) methane, di (4-amino-cyclohexyl) -methane, 2,2-di- (aminophenyl ) -propane or 2,2-di- (4-aminocyclohexyl) -propane and p-phenylenediamine.
• Preferred polyamides are Polyhexamethylenadipin Textreamid (PA 66) and Polyhexamethylensebacin Textreamid (PA 610), polycaprolactam (PA 6) and copolyamides 6/66, in particular with a share of 5 to 95 wt .-% of caprolactam units. PA 6, PA 66 and Copolyamide 6/66 are particularly preferred.
• polyamides may also be mentioned which are obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4,6). Production processes for polyamides of this structure are described, for example, in US Pat EP-A 38 094 . EP-A 38 582 and EP-A 39 524 described.
• polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers, or mixtures of several polyamides, the mixing ratio being arbitrary.
• the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444 ).
• the production of partially aromatic copolyamides with a low triamine content can according to the in the EP-A 129 195 and 129 196 described method.
• For partially aromatic polyamides can also on WO 2008/074687 to get expelled.
• Polyamide-6, polyamide-66 or MXD6-polyamide (adipic acid / m-xylylenediamine) are particularly preferably used.
• the z. B. have at least three carboxyl or amino groups
• Monomers capable of attachment to carboxyl or amino groups e.g. Example, by epoxy, hydroxyl, isocyanato, amino and / or carboxyl groups, and having functional groups selected from hydroxyl, ether, ester, amide, imine, imide, halogen, cyano and Nitro groups, CC double or triple bonds,
• polymer blocks which are capable of attachment to carboxyl or amino groups, for example poly-p-aramidoligomers.
• the property spectrum of the polyamides produced can be adjusted freely within wide limits.
• triacetonediamine compounds can be used as functionalizing monomers. These are preferably 4-amino-2,2,6,6-tetramethylpiperidine or 4-amino-1-alkyl-2,2,6,6-tetramethylpiperidine in which the alkyl group has 1 to 18 carbon atoms or is replaced by a benzyl group.
• the triacetonediamine compound is present in an amount of preferably 0.03 to 0.8 mol%, more preferably 0.06 to 0.4 mol%, each based on 1 mol of acid amide groups of the polyamide.
• DE-A-44 13 177 can be used as functionalizing monomers.
• Component A may also contain at least one further blend polymer in addition to one or more polyamides or copolyamides.
• the proportion of the blend polymer in component A is preferably 0 to 60 wt .-%, particularly preferably 0 to 50 wt .-%, in particular 0 to 40 wt .-%.
• its minimum amount is preferably 5% by weight, more preferably at least 10% by weight.
• natural or synthetic rubbers acrylate rubbers, polyesters, polyolefins, polyurethanes or mixtures thereof may be used as the blend polymer, if appropriate in combination with a compatibilizer.
• Useful synthetic rubbers include ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR), hydrin rubber (ECO), acrylate rubbers (ASA). to be named. Silicone rubbers, polyoxyalkylene rubbers and other rubbers can also be used.
• EPDM ethylene-propylene-diene rubber
• SBR styrene-butadiene rubber
• BR butadiene rubber
• NBR nitrile rubber
• ECO hydrin rubber
• ASA acrylate rubbers
• thermoplastic polyurethane TPU
• SBS styrene-butadiene-styrene block copolymer
• SIS styrene-isoprene-styrene block copolymer
• SEBS styrene-ethylene-butylene-styrene block copolymer
• SEPS block copolymers
• resins may be used as blend polymers, such as urethane resins, acrylic resins, fluorine resins, silicone resins, imide resins, amide-imide resins, epoxy resins, urea resins, alkyd resins or melamine resin.
• ethylene copolymers for example copolymers of ethylene and 1-octene, 1-butene or propylene, as described in US Pat WO 2008/074687 are described.
• the molecular weights of such ethylene- ⁇ -olefin copolymers are preferably in the range of 10,000 to 500,000 g / mol, preferably 15,000 to 400,000 g / mol (number average molecular weight). It is also possible to use pure polyolefins such as polyethylene or polypropylene.
• EP-B-1 984 438 DE-A-10 2006 045 869 and EP-A-2 223 904 to get expelled.
• thermoplastic resins are in the JP-A-2009-155436 listed in paragraph [0028].
• component A it is also possible to use polyesters, polyacetals and polysulfones.
• any suitable dicarboxylic acid may be reacted with any suitable diols.
• convertible dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, undecane-alpha, omega-dicarboxylic acid, dodecane-alpha, omega-dicarboxylic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid , cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid, and cis- and trans-cyclopentane-1,3-dicarboxylic acid.
• dicarboxylic acids can also be used in substituted form.
• ethylenically unsaturated acids such as maleic acid or fumaric acid
• aromatic dicarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid.
• Succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid or their mono- or dimethyl esters are particularly preferably used.
• the diols used are, for example, ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2 , 3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2,3-diol, pentane-2,4 -diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane-1,6-diol, hexane-2,5-diol , Heptane-1,2-dio
• One or both hydroxyl groups in the abovementioned diols can also be substituted by SH groups. Preference is given to ethylene glycol, propane-1,2-diol and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.
• the polyesters preferably have a weight average molecular weight of 500 to 50,000 g / mol.
• Polyacetals which can be used according to the invention are in particular polyoxymethylene homopolymers and polyoxymethylene copolymers. Other polyacetals can be used according to the invention.
• Polysulfones used according to the invention are preferably aromatic polysulfones.
• blend polymers reference may be made to the blend polymers described above for the polyamides. The weight proportions given there for the blend polymers also apply.
• component A is a polyamide and component B is a highly branched or hyperbranched polyethyleneimine or a hyperbranched or hyperbranched polyetheramine.
• component A is a polyester and component B is a highly branched or hyperbranched polycarbonate or a highly branched or hyperbranched polyester.
• the thermoplastic molding compositions contain 0.1 to 15 wt .-% of conductive carbon fillers selected from carbon nanotubes, graphenes, carbon black (in particular conductivity soot), graphite or mixtures thereof. Carbon nanotubes, graphenes or mixtures thereof are preferably contained in an amount of 0.1 to 7 wt .-%, based on the thermoplastic molding composition in this.
• Suitable carbon nanotubes and graphenes are known to those skilled in the art.
• suitable carbon nanotubes can DE-A-102 43 592 , in particular paragraphs [0025] to [0027] are referred to, further on EP-A-2 049 597 especially on page 16, lines 11 to 41, or on DE-A-102 59 498 , Paragraphs [0131] to [0135].
• suitable carbon nanotubes are described in WO 2006/026691 , Paragraphs [0069] to [0074].
• Suitable carbon nanotubes are also shown in FIG WO 2009/000408 , Page 2, line 28 to page 3, line 11 described.
• Carbon nanotubes in the context of the present invention are carbon-containing macromolecules in which the carbon has (mainly) graphite structure and the individual graphite layers are arranged in a tubular manner. Nanotubes and their synthesis are already known in the literature (for example J. Hu et al., Acc. Chem. Res. 32 (1999), 435-445 ). In principle, any type of nanotube can be used in the context of the present invention.
• the diameter of the individual tubular graphite layers is 4 to 20 nm, in particular 5 to 10 nm.
• Nanotubes can be divided into so-called single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). differ.
• SWNTs single-walled nanotubes
• MWNTs multi-walled nanotubes
• the outer shape of the tubes may vary, this may have a uniform diameter inside and outside, but there are also knot-shaped tubes and worm-like structures (vermicular) produced.
• the aspect ratio (length of the respective graphite tube to its diameter) is at least> 10, preferably> 5.
• the nanotubes have a length of at least 10 nm.
• MWNTs are preferred as component B).
• the MWNTs have an aspect ratio of about 1000: 1 and an average length of about 10,000 nm.
• the BET specific surface area is generally from 50 to 2000 m 2 / g, preferably from 200 to 1200 m 2 / g.
• the impurities (eg metal oxides) produced during the catalytic preparation are generally from 0.1 to 12%, preferably from 0.2 to 10%, according to HRTEM.
• Suitable nanotubes can be obtained under the name "multiwall” from the company Hyperion Catalysis Int., Cambridge MA (USA) (see also US Pat EP 205 556 . EP 969 128 . EP 270 666 . US 6,844,061 ).
• Suitable graphenes are described, for example, in Macromolecules 2010, 43, pages 6515-6530 ,
• thermoplastic molding compositions according to the invention may also contain further additives such as further fillers, for. Glass fibers, stabilizers, antioxidants, anti-heat and ultraviolet light decomposition agents, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
• these other additives are present in amounts of from 0 to 50% by weight. , preferably 0 to 35 wt .-% before.
• the invention also relates to a process for the preparation of the above-described thermoplastic molding compositions by mixing the components, preferably in an extruder.
• thermoplastic molding compositions according to the invention takes place for. B. by extrusion process at temperatures customary for thermoplastic processing. For example, it can be a like in DE-A-10 2007 029 008 described method are used. Furthermore, for the production on WO 2009/000408 to get expelled.
• the preparation is preferably carried out in a co-rotating twin-screw extruder in which components B and C are introduced into component A.
• the component C can be introduced as a powder or in the form of a masterbatch in thermoplastic molding material.
• the feeding of the component B can take place independently of the feed of the conductive filler of the component C, for example in the "hot feed" of the extruder.
• a component B containing masterbatch can be used. It is also possible to add components B and C mixed.
• thermoplastic molding composition can be carried out by known methods, for example by injection molding or compression molding.
• the inventive method allows the production of filled with the carbon fillers of component C thermoplastic molding compositions with low energy consumption at good dispersion levels.
• thermoplastic molding compositions or molded articles produced therefrom become antistatic or conductive.
• antistatic volume resistances of 10 9 to 10 8 ohm cm are understood.
• conductive volume resistances of less than 10 6 ohm cm are understood.
• novel thermoplastic molding compositions are used in particular for the production of conductive moldings.
• the invention also relates to moldings of the above-described thermoplastic molding composition.
• the polycarbonates were analyzed by gel permeation chromatography using a refractometer as detector. Dimethylacetamide was used as the mobile phase and polymethyl methacrylate (PMMA) was used as the standard for determining the molecular weight.
• PMMA polymethyl methacrylate
• TMP x 1.2 PO describes therein a product which has been reacted per mole of trimethylolpropane with an average of 1.2 moles of propylene oxide.
• the viscosity number of the polyamide VN was determined according to ISO 307 in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C.
• the MFR of polyethylene was determined to ISO 1133 at 190 ° C under a load of 2.16 kg.
• the electrical conductivity was measured as volume conductivity using a 4-point measuring apparatus. For each plate, the measurement was made on five 77 x 12 x 4 mm 3 samples sawn from hardened plates. In order to achieve a good contact between sample and electrodes, four silver electrodes were painted directly onto the sample using a conductive silver paste (Leitsilber 200 from Hans Wohlbring GmbH). The current source used was 225 Current Source, the 617 Programmable Electrometer and the Keithley Instruments 1000 Multimeter.
• the masterbatches were diluted with nylon-6 and introduced with the other for compounding in a DSM 15 extruder.
• the extrusion was carried out at a melting temperature of 270 ° C, a rotational speed of 80 U / min and a residence time of 5 minutes.
• the samples were then injection molded as plates measuring 30 x 30 x 1.27 mm 3 for conductivity measurement.
• the injection-molded plates were produced on an Xplor forming machine 12 mL at a melting temperature of 270 ° C., a mold temperature of 80 ° C., an injection pressure of 12 to 16 bar and a repetition time of 15 seconds.
• Table 1 The composition of the molding compositions and the determined volume resistivity are summarized in Table 1 below.
• the preparation of the carbon-filled molding compositions was carried out with a ZSK extruder from Coperion with a screw diameter of 18 mm.
• the extruder had 11 zones, the polymer being cold filled in zones 0 and 1. Zones 2 and 3 served to melt and transport. In zone 4, the hyperbranched polymer was added via a hot feed.
• the following zones 5 and 6 were used for dispersion, with part of zone 6 together with zone 7 also serving for homogenization.
• zones 8 and 9 a redispersion was carried out. This was followed by a zone 10 for degassing and zone 11 for discharge.
• the hyperbranched polymer entry into zone 4 was made using a gear pump.
• the extruder throughput was set at 5 kg / h and the screw speed was kept constant at 400 rpm.
• the extrusion temperature was 260 ° C.
• the products were granulated and processed by injection molding. The injection molding was carried out on an Arburg 420C at a melt temperature of 260 ° C and a mold temperature of 80 ° C.
• Table 3 sample A C B volume resistivity Wt .-% Wt .-% Wt .-% (Ohm cm) injection compression Ref. 6 A1 97 C3 3 1,73E + 02 9.2E + 00 Ex. 8 A1 94 C3 3 B1 3 1,21E + 03 1.1E + 01 Ex. 9 A1 94 C3 3 B2 3 9,27E + 02 9,3E + 00 Ex. 10 A1 96 C3 3 B1 1 2,26E + 03 1.0E + 01 Ex. 11 A1 96 C3 3 B2 1 7,95E + 10 7,03E + 03
• the volume resistivities for the compression molded articles were significantly lower than the molded articles produced by injection. Without wishing to be bound by theory, it is possible that longitudinal orientation of the fillers occurs in the moldings produced by injection so that less network formation occurs.
• the molding compositions containing carbon fillers have a considerably lower volume resistance in comparison to the molding compositions which contain only the hyperbranched polymers.
• Table 5 summarizes the volume resistivities for PBT-containing samples. They were prepared according to method 2. Here, samples containing hyperbranched polymers are compared with samples that do not contain hyperbranched polymers. The results are summarized in Table 5: Table 5: sample A C B volume resistivity Wt .-% Wt .-% Wt .-% (Ohm cm) Ref. 10 A3 98 C4 2 6.0E + 03 Ex. 20 A3 97 C4 2 B3 1 1.7E + 03 Ref. 11 A3 99 C4 1 6,4E + 11 Ex. 21 A3 98 C4 1 B3 1 1.5E + 06

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• 2012
  • 2012-01-17 CN CN2012800134274A patent/CN103443204A/zh active Pending
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